TWI417375B - A method for removing sulfides from a liquid fossil fuel and the device using the same - Google Patents

Description

Desulfurization method for fossil fuel and device using the same

This invention relates to a method of defluxing petroleum, fossil fuels, and petroleum-based fuels.

In the current transportation industry, diesel fuel is a widely used fossil fuel. Since diesel engines have advantages over gasoline engines in terms of energy saving, today's demand for diesel fuel is expected to rise in the future due to the growing awareness of environmental protection and green sports. Diesel fuels are generally a relatively complex mixture of alkane, naphthenic, and aromatic hydrocarbons having a carbon number between 9 and 28 and a boiling point in the range of about 150-390 °C. Their relative distribution is largely determined by factors such as specific fuel feedstocks, refining procedures, and hybrid programs based on the consumer's daily business needs. Sulfides which are more commonly found in diesel fuels are, for example, alkylbenzothiophenes and alkyldibenzothiophenes.

The presence of sulfur in diesel fuel can cause environmental problems. For example, when burning, sulfur dioxide (SO ₂ ) and sulfate particulate matter are produced, which are serious harmful substances and cause great harm to public health. Moreover, sulfur can cause other problems, such as damage to the catalytic converter, partial corrosion of the internal combustion engine, and increasing air pollution. Also, because the sulfur contained in gasoline and other petroleum products poses a hazard to the outside world, the US Environmental Protection Agency has issued regulations to reduce the upper limit of sulfur content of petroleum from the original 300 ppm. 30 ppm, while the upper limit of sulfur content of diesel is reduced from the original 500 ppm to 15 ppm to ensure the safety and health of the public.

The hydrodesulfurization process is a desulfurization process which removes sulfur from diesel fuel on a large scale in a conventional chemical manner. The conventional hydrodesulfurization process is a hydro-treatment process in which a sulfur-containing compound in diesel is decomposed by hydrogen and a catalyst to form hydrogen sulfide.

However, even a small amount of unreacted hydrogen sulfide in the desulfurization process can cause great harm. Hydrogen sulphide is quite toxic and has caused a large number of deaths in the workplace, which poses a considerable threat to workers. In addition, under the new and stricter regulations of the US Environmental Protection Agency, the probability of hydrogen leaking from the outer wall of the reactor will be higher when the hydrodesulfurization process is implemented.

Oxidative desulfurization is a conventional desulfurization method suitable for diesel fuel. The method is based on the following principle of operation: the sulfur compound has a higher polarity than the hydrocarbon. In addition, sulfur oxides, such as ruthenium, are also more polar than sulfides. More importantly, oxidation from sulfide to helium is also faster and easier than hydrocarbons. Therefore, the conversion of less polar sulfides to more polar sulfonium or sulfoxide allows the sulfur compounds to be easily extracted from fossil fuels and dissolved in the aqueous phase solution.

In U.S. Patent No. 6,402,939, the following technical solution is described to remove organic sulfur compounds from fossil fuels by combining oxidative desulfurization and ultrasonic techniques. Among them, the oxidative desulfurization method is achieved by combining the fossil fuel in the aqueous phase fluid with the hydroperoxide as the oxidizing agent, and the ultrasonic wave is applied to the mixture to increase the reactivity of various substances in the mixture. Ultrasound-assisted oxidative desulfurization (UAOD) is carried out at normal temperature and pressure, which allows sulfur compounds to be selectively removed from hydrocarbons. However, the use of quaternary ammonium bromides as a surfactant produces by-products such as bromide. In addition, the sonoactor used in the desulfurization process also has a number of disadvantages, such as the need for extremely expensive instruments that require technically complex parts such as RF amplifiers and function generators, in addition to generating super Sound waves also require higher power consumption, and require higher operating temperatures (usually at 70-80 ° C), and long-term ultrasonic waves can also cause damage to long-chain hydrocarbons (eg, cracking). In addition, the corresponding function generator and RF amplifier need to be increased to be suitable for larger-scale production, which also causes a limitation in mass production of the conventional ultrasonic reactor or ultrasonic desulfurization device.

Moreover, in batch production, the use of probe type reactors and the application of ultrasonic waves in the oxidative desulfurization mode can increase the sulfur removal rate, but all the reactants must be combined and Keep in a controlled environment for a while until the desired reaction results are achieved. As such, such reaction procedures tend to be slower, take more time, and the production must be in a separate state before the end of the process.

In order to overcome the above problems, it is an object of the present invention to provide a mixed assisted oxidative desulfurization method suitable for use in fossil fuels. The above fossil fuel is combined with an aqueous phase oxidizer solution comprising a hydroperoxide solution or an ozone solution. The aqueous phase oxidant solution comprises a quaternary ammonium salt as a surfactant which is composed of a positively charged nitrogen atom having four substituents and is combined with a negatively charged counterion. Compound. In this embodiment, the quaternary ammonium salt has at least one carbon chain comprising more than 8 carbon atoms. The quaternary ammonium salt acts as a surfactant to increase the yield of sulphide to hydrazine without the formation of by-products such as bromide.

Another object of the present invention is to provide a mixed assisted oxidative desulfurization process suitable for use in fossil fuels. The fossil fuel described above is combined with an aqueous phase hydroperoxide solution or an aqueous phase ozone solution. The hydroperoxide solution or ozone solution comprises a quaternary ammonium salt which acts as a surfactant to increase the yield of sulphide in the organic phase fuel to hydrazine. The hybrid assisted oxidative desulfurization process uses multiple mixing tanks and multiple cyclones without the need to use any complex, unreliable, and expensive ultrasonic generator. In addition, since no ultrasonic generator is used, it is not necessary to use a refrigerant in the degassing process of the fossil fuel to cool the multiphase reaction medium. Moreover, this mixed assisted oxidative desulfurization process requires much less energy. In addition, because it does not require the use of a function generator and an RF amplifier, the hybrid assisted oxidative desulfurization method is more suitable for large-scale production than conventional ultrasonic generators or ultrasonic desulfurization methods. Moreover, this mixed assisted oxidative desulfurization process does not cause damage to long-chain hydrocarbons (for example, cracking).

It is yet another object of the present invention to provide a continuous flow system for oxidative desulfurization of fossil fuels. The oxidative desulfurization system is a continuous flow unit having a plurality of modular mixing tanks including at least two mixing tanks, a mixer, at least two cyclones, and an evaporation tower. The mixer is connected to each mixing tank for agitation and mixing to effectively produce an emulsified foam, and the cyclone is continuously connected in series with the mixing tank. The evaporation tower is connected to one of the cyclones and one of the mixing tanks to generate helium. In addition, in order to process more fuel and increase oxidation, a plurality of sets of mixing tanks and cyclones may be added, which are connected or connected in series with a plurality of evaporation towers, respectively.

The above described objects, features, and advantages of the present invention will become more apparent from the following description.

Many deep desulfurization methods have to be costly. Over the past four decades, scientists have tried to develop many deep desulfurization alternatives. Among them, oxidative desulfurization is a low-cost, high-efficiency deep desulfurization technology. Oxidative desulfurization must choose appropriate catalyst and strong oxidant, with appropriate surfactant, which can greatly improve the desulfurization efficiency of oil; the reaction process is: convert the organic sulfur in the oil into polar sulfur oxide, The sulfur is removed with a polar solvent/adsorbent.

Here, the hydroperoxide refers to a compound in which R in the molecular structure represents a hydrogen atom, an organic group, or an inorganic group. Wherein the hydroperoxide wherein R is an organic group is soluble in water, and is, for example, methyl hydroperoxide, ethyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide , Dibutyl hydroperoxide, tributyl hydroperoxide, 2-methoxy-2-propyl hydroperoxide, tripentyl hydroperoxide ( Tert-amyl hydroperoxide), and cyclohexyl hydroperoxide. Further, the hydroperoxide in which R is an inorganic group is, for example, peroxynitrite, perphosphoric acid, and persulfuric acid. Preferred hydroperoxides are hydrogen peroxide (wherein R is a hydrogen atom) and a trialkyl peroxide such as tributyl peroxide.

The fossil fuel is mixed with an oxidizer aqueous solution to form an aqueous fluid, wherein the oxidant aqueous phase solution comprises hydrogen peroxide, hydroperoxide, or ozone. The relative ratio of liquid fossil fuel to oxidant aqueous phase solution is between about 1:1 and 1:3, preferably about 1:1.25. In the aqueous oxidant solution, the concentration of hydroperoxide is between 1% and 30%. Although the relative proportions affect the procedural effectiveness and ease of fluid handling, it is not critical in the present invention. However, in most cases, the addition of ozone to the aqueous oxidant solution produces better results. For example, ozone is added to the water by an ozone generator (model: Pacific Ozone L22). The phase liquid or ozone is directly driven into the solution. Among them, the flow rate of ozone is mainly between 0.01 g/hr and 1 g/hr. Further, the concentration of ozone in the aqueous oxidant solution is between 0.01 g/L and 1 g/L, and is preferably in a saturated state.

The content of hydroperoxide relative to fossil fuel and aqueous phase solutions may still vary, although the conversion rate may only vary slightly with the proportion of hydroperoxide. When the hydroperoxide is hydrogen peroxide and its volume is relatively between about 1% and 30% of the total aqueous phase and the organic phase solution, a preferred ratio is 3% to 30% for better results. For other hydroperoxides other than hydrogen peroxide, the preferred relative volume is the corresponding molar amount.

In this embodiment, a metal catalyst is included in the reaction system to regulate the activity of hydroxyl radicals which are produced by hydroperoxides. The metal catalyst is, for example, transition metal catalysts, Fenton catalysts, or metal ion catalysts, and the metal of the above metal ion catalyst. The ions are, for example, iron II ions, iron III ions, copper I ions, copper II ions, chromium III ions, chromium VI ions, molybdenum ions, tungsten ions, and vanadium ions. For some systems, such as crude oil systems, Fenton catalysts are preferred. For other systems, such as diesel systems and other systems where diphenylthiophene is an important constituent, tungstate is the preferred metal catalyst. Wherein the tungstate comprises tungstic acid, substituted tungstic acids, or a metal tungstate, such as phosphotungstic acid. The above-mentioned metal catalyst must be added in an amount to achieve a catalytically effective amount, and the so-called catalytically effective amount means an amount which can react the reaction process toward a predetermined target (i.e., oxidize sulfide to ruthenium). In most cases, when the hydroperoxide solution is 25 grams, the catalytically effective amount is from 0.01 grams to 0.5 grams (about 3% to 30% by volume), preferably 0.2 grams. In this embodiment, the surfactant is a Tetraoctylphosphonium salt, and the tetraoctylphosphonium salt is, for example, tetraoctylphosphonium bromide, tetraoctylphosphonium chloride, tetraoctylphosphonium iodide, or tetra. Phosphate octyl acetate, or tetraoctyl chromium phosphate. The chemical structural formula of the above tetraoctylphosphonium salt is as follows:

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are alkyl radicals, and have 8 carbon atoms in the alkyl branch and the alkyl straight chain, and X ⁻ is an anion. In most cases, when the hydroperoxide solution is 25 grams, the catalytically effective amount of the tetraoctylphosphonate as a surfactant is between 0.01 and 0.5 grams (about 3% to 30% by volume). Concentration), preferably 0.2 g. The oxidant aqueous phase solution, the surfactant, the metal catalyst, and the higher sulfur content diesel are mixed through a plurality of conduits and transported to the first mixing tank. With conventional flow valve and flow control systems, the flow of feed streams in each conduit can be independently controlled. In the first mixing tank, these reactants can be thoroughly mixed by means of a mixer. In addition, in the oil/aqueous emulsion of the oil phase/water phase in the first mixing tank, the contact area produced by the plurality of foams increases the reaction rate of oxidation of the sulfide to the hydrazine or hydrazine.

When the reaction mixture is completed, the resulting mixture will include an aqueous phase and an organic phase, wherein the organic phase includes most of the ruthenium formed by oxidation. The resulting mixture is phase separable prior to removal of the crucible. The action of phase separation can be accomplished by deemulsion. In addition, the procedure for breaking the emulsion can be accomplished in a conventional manner. These methods are apparent to those of ordinary skill in the art of operating emulsification and continuous agitation, particularly in the field of oil-in-water emulsions.

Compared with the sulfides originally present in fossil fuels, ruthenium has a higher polarity. Therefore, after the polar substances are mixed and separated by a polar solution extractor, the ruthenium can be easily removed from the aqueous phase, the organic phase, Or a mixture of the two removed. In this embodiment, the polar solution extractor is a mixing tank equipped with a mixer. The addition of numerous microfoams to a well-stirred and mixed emulsified mixture increases the benefit of the extraction because the contact area of the polar solution with the fossil fuel is increased. These tiny foams may be liquid bubbles or gas foams such as oil phase foams or aqueous phase foams. In other embodiments, the polar solution extractor can be a liquid-solid adsorption unit. Alumina can be packed into the column of the solid state adsorption unit and can be assisted by gravity and vacuum techniques to aid the absorption process. In a polar solution extractor, a solution such as acetonitrile can be used as a polar solution. The acetonitrile can be easily separated from the hydrazine by distillation (boiling point between about 550 K and 950 K). Among them, the weight percentage of solvent and oil can be maintained at 1:1 (for example: 1 gram of diesel with 1 gram of acetonitrile).

Here, "liquid fossil fuel" means any carbon-containing liquid extracted from petroleum, coal, and other natural materials. These fuels may be fuels for vehicles such as gasoline, diesel, aircraft fuels, rocket fuels, or petrochemical residual fuel oils such as heavy oils and surplus fuels.

The hybrid assisted oxidative desulfurization process is carried out, for example, by using a continuous flow system which can be operated in a steady state in which the reactants are continuously input into a reaction vessel, and The product is continuously removed from the reaction vessel.

The embodiment discloses a continuous desulfurization device 10, which can process a large amount of diesel fuel in a short time, and has the advantages of high desulfurization efficiency, low capital investment, and low maintenance cost. Moreover, the operating temperature of the continuous desulfurization apparatus 10 is lower than that of the ultrasonic generator. Generally, the operating temperature can be raised to about 50-60 ° C due to the chemical reaction of the aqueous phase fluid. This continuous desulfurization unit 10 can remove about 95% of the sulfur content. To increase the yield and efficiency, two continuous desulfurization units 10 can be connected in parallel to achieve a higher desulfurization rate.

FIG. 1 illustrates the continuous desulfurization apparatus 10 of the present embodiment. Among them, the oxidant supply tank 30 is for supplying the oxidant aqueous phase solution, and the diesel feed tank 20 is for supplying the diesel fuel having a high sulfur content. The oxidant supply tank 30 and the diesel feed tank 20 are connected to the first mixing tank 100 by a plurality of conduits. In addition, the surfactant container 40 and the metal catalyst container 50 are also connected to the first mixing tank 100. Here, the flow rates of the oxidant supply tank 30, the diesel feed tank 20, the surfactant container 40, and the metal catalyst container 50 can be individually and independently controlled by a conventional flow valve and flow rate control system.

The mixture participating in the reaction is mixed in the first mixing tank 100 by adding a surfactant and a metal catalyst, and with the aid of the mixer 110. Here, the first mixing tank 100 can also be regarded as a desulfurization reactor. The reactive mixing procedure carried out in the emulsion of the oil phase/water phase of the first mixing tank 100 includes a procedure for oxidizing the sulfide to the hydrazine and hydrazine. After mixing, the mixture participating in the reaction is transported to the first cyclone separator 140. The first cyclonic separator 140 can be considered a diesel/aqueous phase separation tank. In this diesel/water phase separation tank, the aqueous phase fluid (containing the oxidant and catalyst) is separated from the oil phase fluid (including diesel and helium). Thereby, in the subsequent processing procedure, diesel having a low sulfur content can be produced. Thereafter, after a period of time, the aqueous phase fluid is recirculated to the first mixing tank 100 via the recycle loop and through the catalyst activation vessel 55.

In the present embodiment, the mixer 110 is a mechanically agitated mixer that mixes the solution in the first mixing tank 100 by means of mechanical agitation. However, those skilled in the art can also use a mixer that achieves mixing effects such as an ultrasonic oscillator or a high-pressure water column mixer. The so-called high-pressure water column mixer uses a jet of high-pressure water column to achieve mixing.

A second mixing tank 200 is disposed between the first cyclone separator 140 and the second cyclone separator 240. The second mixing tank 200 is a polar solution extractor. In the second mixing tank 200, after the mixing and extraction process by the mixer 110, a by-product such as hydrazine and diesel having a low sulfur content are contained. The oil phase fluid is separated. Thereafter, the above-described oil phase fluid is sent to the second cyclone separator 240, which separates the low sulfur content diesel oil and stores it in the diesel holding tank 11. Further, a polar solution containing by-products such as ruthenium is transferred to an evaporation tower 300 to recover and reuse the polar solution and store it in a solution recovery tank 65. Among them, by-products such as hydrazine can be obtained from the evaporation tower 300.

For various fuels with different sulphur content, an optimized mixed-assisted oxidative desulfurization procedure can remove more than 95% of the sulfur, or reduce the sulfur concentration to less than 15 ppm. Further, the use of a tetraoctylphosphine salt can also prevent the production of by-products such as bromide. Moreover, the better phase-to-phase conversion capability also allows the excessive metal catalyst to have a higher recovery rate and better reuse rate, so even with the diluted hydroperoxide and ozone solution, the same desulfurization can be obtained. effectiveness.

Please refer to FIG. 2. FIG. 2 illustrates a desulfurization procedure of the portable continuous desulfurization apparatus of FIG. 1. The desulfurization procedure removes sulfur from the liquid fossil fuel, which includes the following steps.

In step S100, the liquid fossil fuel flowing out from the diesel supply tank 20 is mixed with an oxidizing agent solution flowing out from the oxidizing agent supply tank 30, which is an ozone solution or a hydrogen peroxide solution including water. Further, the surfactant stored in the surfactant container 40 is mixed with the metal catalyst stored in the metal catalyst container 50 to form a multiphase reaction medium. a surfactant, for example, a tetraoctylphosphonium salt having four substituents, and the substituent is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl group. A material in which at least one substituent is an alkyl group having 8 or more carbon atoms. The metal catalyst stored in the metal catalyst container 50 is an excessive metal catalyst such as phosphotungstic acid. Moreover, for example, in every 25 grams of sulfur-containing diesel fuel as a liquid fossil fuel, the amount of surfactant used is about 0.1 gram, the amount of metal catalyst used is about 0.2 gram, and the collocation is the same as that of sulphur-containing diesel. A volume of aqueous solution of hydrogen peroxide or ozone, wherein the volume concentration of hydrogen peroxide or ozone is between 3% and 30%.

In step S105, the heterogeneous reaction medium is subjected to reactive mixing for a sufficient period of time to oxidize the sulfide in the diesel to ruthenium and form an emulsion bubble. By sufficiently stirring and mixing the multi-phase reaction medium in the first mixing tank 100, the diameter of the foam produced can be less than 1 mm, or the diameter of most of the foams is less than 1 mm, preferably. In the case, the majority of the foam is maintained at a diameter of about 10 microns, and the remainder of the foam has a diameter of less than about 0.1 mm.

In step S110, the oil phase fluid can be separated from the aqueous phase fluid by the first cyclone separator 140. Thereafter, in step S130, the solution containing the polar solvent can be separated from the non-polar solution by the second cyclone 140.

In step S115, the oil phase fluid in the polar solvent can be mixed and separated by the second mixing tank 200, also referred to as a polar solution extractor. The polar solvent in the second mixing tank 200 is, for example, acetonitrile, and in the case of a boiling point of 550 K to 950 K, acetonitrile can be easily separated from the crucible by distillation. The weight percentage of solvent to oil is maintained at 1:1, for example: 1 gram of diesel with 1 gram of acetonitrile. The plurality of emulsified foams formed are all less than 1 mm in diameter, or most of the foams are less than 1 mm in diameter. In preferred cases, most of the foam has a diameter of about 10 microns, and most of the rest The foam has a diameter of less than about 0.1 mm. In step S105 and step S115, the generated foam may be a bubble or an immiscible liquid foam.

In step S120, the surfactant and the metal catalyst are collected by the first cyclone 140 and recycled in the catalyst activation vessel 55. At the same time, in step S125, the solvent used in the second mixing tank 200, for example, acetonitrile, can be collected and recovered by the distillation procedure in the evaporation tower 300.

In step S140, the by-products such as helium in the second mixing tank 200 and the second cyclone separator 240 can be separated from the polar fluid and the non-polar fluid by the evaporation tower 300. In step S150, helium is transferred from the evaporation tower 300 to the crucible holding vessel 70. Thereafter, in step S135, the non-polar and non-deuterium-containing organic fluid is collected in the clean diesel holding tank 11.

The present invention has been described above by way of examples, and is not intended to limit the scope of the claims. The scope of patent protection is subject to the scope of the patent application and its equivalent fields. Modifications or modifications made by those skilled in the art, without departing from the spirit or scope of the invention, are equivalent to the equivalents or modifications made in the spirit of the invention and should be included in the following claims. Inside.

10. . . Continuous desulfurization device

11. . . Diesel retention tank

20. . . Diesel supply tank

30. . . Oxidizer supply tank

40. . . Surfactant container

50. . . Metal catalyst container

55. . . Catalyst activation container

65. . . Solution recovery tank

70. . .碸 keep container

100. . . First mixing tank

200. . . Second mixing tank

110. . . mixer

140. . . First cyclone separator

240. . . Second cyclone separator

300. . . Evaporation tower

S100~S150. . . Flow chart step

FIG. 1 illustrates the continuous desulfurization apparatus of the present embodiment.

2 is a desulfurization procedure of the portable continuous desulfurization apparatus of FIG. 1.

S100~S150. . . Flow chart step

Claims (28)

A method of removing sulfide from a liquid fossil fuel, comprising: (a) combining an oxidant solution, a metal catalyst, and a surfactant to form a heterogeneous reaction medium; and (b) in a desulfurization reactor And reacting the heterogeneous reaction medium for a sufficient period of time to oxidize the sulfide in the liquid fossil fuel to ruthenium, and further forming a plurality of foams in the desulfurization reactor to increase the reaction area and promote the reaction efficiency. . The method of removing sulfides according to claim 1, further comprising: separating the oil phase fluid from the aqueous phase fluid using a first cyclone. The method for removing sulfides as described in claim 2, further comprising: mixing the oil phase fluids and separating them from the polar solvent fluid by a polar solution extractor. The method for removing sulfides as described in claim 3, further comprising: producing a plurality of foams in a polar solution extractor, most of which have a diameter of less than 1 mm. The method for removing sulfides according to claim 2, further comprising: recycling the aqueous solvent solution containing the surfactant, the oxidant solution, and the metal catalyst. The method of removing sulfides as described in claim 2, further comprising: separating the oil phase fluid from the polar solvent fluid using a second cyclone. The method of removing sulfides as described in claim 6 further comprises: separating and agglomerating the crucible to produce an organic phase fluid substantially free of rhodium. The method for removing sulfides according to claim 1, wherein the surfactant is a quaternary ammonium salt having four substituents, and the substituents are selected from the group consisting of A material of a group consisting of an alkyl group, an aryl group, and an aralkyl group of 20 carbon atoms, wherein at least one of the substituents is an alkyl group having 8 or more carbon atoms. A method of removing sulfides as described in claim 8 wherein the surfactant is a tetraoctylphosphonium salt. The method of removing sulfides according to claim 1, wherein the oxidant solution comprises hydrogen peroxide, hydroperoxide, or ozone. The method of removing sulfides according to claim 1, wherein a mixing ratio of the liquid fossil fuel to the oxidant solution is between about 1:1 and 1:3. The method for removing sulfides according to claim 1, wherein the metal catalyst is selected from the group consisting of iron II ion compounds, iron III ion compounds, copper I ion compounds, copper II ion compounds, chromium III ion compounds, and chromium. A material of a group consisting of a IV ion compound, a molybdate, a tungstate, and a vanadate, the metal catalyst forming a heterogeneous reaction medium together with a liquid fossil fuel and an oxidant solution. A method of removing sulfides as described in claim 12, wherein the metal catalyst is phosphotungstic acid. The method of removing sulfides according to claim 1, wherein the liquid fossil fuel is selected from the group consisting of crude oil, shale oil, diesel, gasoline, kerosene, liquefied petroleum gas, and petrochemical residual fuel oil. A method of removing sulfides as described in claim 1, wherein the liquid fossil fuel is a diesel or diesel fuel blend. A method of removing sulfide from a liquid fossil fuel, comprising: (a) combining an oxidant solution, a metal catalyst, and a surfactant to form a heterogeneous reaction medium, wherein the oxidant solution comprises ozone; and (b) The reaction medium of the heterogeneous reaction medium is mixed for a sufficient period of time to oxidize the sulfide in the liquid fossil fuel to hydrazine. A method of removing sulfide from a liquid fossil fuel, comprising: (a) combining an oxidant solution, a metal catalyst, and a surfactant to form a heterogeneous reaction medium, wherein the surfactant comprises a tetraoctylphosphonium salt (b) reacting the heterogeneous reaction medium for a sufficient period of time to oxidize the sulfide in the liquid fossil fuel to ruthenium. A continuous desulfurization device comprising: a plurality of mixing tanks, each mixing tank being connected with a mixer for stirring and mixing to produce a plurality of foams, most of which have a diameter of less than 1 mm; a plurality of cyclones, each of which is connected in series with the mixing tank; an evaporation tower connected to one of the cyclones, the cyclone being used to generate substantially flawless The organic phase. The continuous desulfurization apparatus according to claim 18, wherein the mixer is connected to the mixing tank, and the mixing tank is connected to a recirculation circuit. The continuous desulfurization apparatus according to claim 18, further comprising: a diesel supply tank, wherein the diesel fuel supply tank contains a high sulfur content diesel fuel; and an oxidant supply tank in the oxidant supply tank Having an aqueous oxidant solution; a surfactant container containing a surfactant in the surfactant container; and a metal catalyst container containing a metal catalyst in the metal catalyst container; The mixing tank includes a first mixing tank, the plurality of cyclones including a first cyclone, the first cyclone is a diesel/water phase separation tank; the diesel supply tank, the oxidant supply tank, the interface The active agent container and the metal catalyst container are connected to the inlet of the first mixing tank, and the first cyclone separator is connected to the outlet of the first mixing tank. The continuous desulfurization apparatus of claim 20, wherein the aqueous phase fluid separated by the first cyclone is recirculated to the first mixing tank via a recirculation loop. A continuous desulfurization apparatus according to claim 21, wherein a catalyst activation vessel is provided in the recirculation loop. The continuous desulfurization apparatus according to claim 20, wherein the plurality of mixing tanks further comprise a second mixing tank, the plurality of cyclones further comprising a second cyclone, the second mixing tank is A polar solution extractor is coupled between the first cyclonic separator and the second cyclonic separator. The continuous desulfurization apparatus according to claim 23, further comprising a diesel retention tank, wherein the second cyclone separator separates and stores the low sulfur content diesel oil in the diesel retention tank. The continuous desulfurization apparatus according to claim 23, further comprising a recirculation loop connected to the second mixing tank. A continuous desulfurization apparatus as described in claim 25, wherein a solution recovery tank is provided in the recirculation loop. The continuous desulfurization apparatus according to claim 18, wherein the mixer is an ultrasonic oscillator, a mechanical agitating mixer, or a high pressure water column mixer. A continuous desulfurization device comprising: a first mixing tank; a diesel feed tank in which a high sulfur content diesel fuel is contained, the diesel feed tank being connected to the inlet of the first mixing tank An oxidant supply tank, wherein the oxidant supply tank contains an oxidant aqueous phase solution, the oxidant supply tank is connected to the inlet of the first mixing tank; and a surfactant container is accommodated in the surfactant container a surfactant, the surfactant container is connected to the inlet of the first mixing tank; a metal catalyst container containing a metal catalyst in the metal catalyst container, the metal catalyst container being the first The inlet of the mixing tank is connected; a first cyclone separator, the first cyclone separator is a diesel/water phase separation tank and is connected in series with the first mixing tank; a second mixing tank, the second mixing tank The second mixing tank is a polar solution extractor, the second mixing tank is connected to the first cyclone; and a second cyclone separator is connected to the first cyclone, a second cyclone separator for generating an organic phase substantially free of bismuth; an evaporation tower connected to the second cyclone; and a diesel retention tank separated from the second cyclone Connected to each other; wherein the aqueous phase fluid separated by the first cyclone is recirculated to the first mixing tank via a recirculation loop, substantially free of the second cyclone separated The organic phase present in the crucible is transferred to the evaporation tower, and the second cyclone separator separates and stores the diesel fuel having a low sulfur content in the diesel holding tank.